CN106459278B

CN106459278B - Improved catalyst system for the preparation of polyethylene copolymers in a high temperature solution polymerization process

Info

Publication number: CN106459278B
Application number: CN201580020147.XA
Authority: CN
Inventors: 努尔丁·阿杰拉尔; 罗伯塔·佩莱基亚; 卢吉·雷斯科尼; 乌亚特奇斯拉夫·V·依兹默; 德米特里·S·科诺诺维奇; 亚历山大·Z·乌斯科博伊尼科夫
Original assignee: Borealis AG
Current assignee: Borealis AG
Priority date: 2014-04-17
Filing date: 2015-04-15
Publication date: 2020-11-06
Anticipated expiration: 2035-04-15
Also published as: KR102355323B1; RU2016142451A3; WO2015158790A3; JP2017511418A; CN106459278A; WO2015158790A2; ES2770021T3; US10167355B2; US20170037165A1; JP6734783B2; RU2016142451A; EP3131934B1; TW201605913A; EP3131934A2; KR20160147835A; RU2693453C2; TWI547507B

Abstract

A catalyst system for the preparation of ethylene copolymers in a high temperature solution process comprising (I) a metallocene complex of formula (I) wherein M is Hf or Zr, X is a sigma ligand and L is of formula-SiR⁸ ₂A bridge of (a) wherein each R⁸Independently is C₁‑C₂₀-hydrocarbyl, tri (C)₁‑C₂₀Alkyl) silyl, C₆‑C₂₀-aryl, C₇‑C₂₀-aralkyl radical or C₇‑C₂₀-alkylaryl, n is 0,1 or 2, R¹And R^1′Identical or capable of being different and can be linear or branched C₁‑C₆-alkyl radical, R²And R^2′Are the same or different and are CH₂‑R⁹Group, wherein R⁹Is H or straight or branched C₁‑C₆-alkyl radical, R⁵And R^5′Identical or different and can be H or straight-chain or branched C₁‑C₆-an alkyl group OR an OR group, wherein R is C₁‑C₆-alkyl radical, R⁶And R^6′Identical or different and can be H or C (R)¹⁰)₃Group, wherein R¹⁰Are the same or different and R¹⁰Can be H or straight or branched C₁‑C₆-an alkyl group, or R⁵And R⁶And/or R^5′And R^6′Together form an unsubstituted 4-7 membered ring fused to the phenyl ring of the indenyl moiety, provided that if R is⁵And R⁶And R^5′And R^6′Together form an unsubstituted 5-membered ring fused to the phenyl ring of the indenyl moiety, then R²And R^2′Is other than C₁-an alkyl group, and R⁷And R^7′Can be identical or different and can be H or straight-chain or branched C₁‑C₆-an alkyl group; (ii) an aluminoxane cocatalyst; and (iii) optionally a boron-containing promoter.

Description

Improved catalyst system for the preparation of polyethylene copolymers in a high temperature solution polymerization process

Technical Field

The present invention relates to an improved catalyst system capable of producing polyethylene copolymers in a high temperature solution polymerization process. The catalyst system comprises a combination of a selected bis-indenyl metallocene complex substituted in at least the 2-and 4-positions of the two indenyl groups and a cocatalyst mixture comprising an aluminoxane cocatalyst and optionally a further boron-based cocatalyst. These combinations significantly result in catalyst systems with excellent activity, productivity and stability and allow the preparation of polyethylene copolymers with increased comonomer insertion.

Background

Metallocene catalysts have been used for many years to make polyolefins. Numerous academic and patent publications describe the use of these catalysts in the polymerization of olefins. Metallocenes are now used industrially and polyethylene and in particular polypropylene are generally prepared using cyclopentadienyl-based catalyst systems with different substitution patterns.

The use of several of these metallocene catalysts in solution polymerization, in particular for the preparation of polypropylene, has been described.

For example, WO2007/116034 describes a catalyst system comprising racemic dimethylsilylbis (2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl) zirconium dichloride and methylalumoxane cocatalyst for the preparation of polypropylene in a solution polymerization process at temperatures between 100 and 120 ℃.

It is to be mentioned that metallocene compounds can also be used for the preparation of ethylene copolymers, preferably ethylene-butene copolymers, but such copolymers are said to be obtained by using a gas phase process.

WO 2007/122098 also describes the use of complex racemic dimethylsilylbis (2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-benzinden-1-yl) zirconium dichloride in combination with an aluminoxane cocatalyst at 100 ℃ for the preparation of ethylene copolymers.

EP 2532687A describes another class of metallocene complexes, such as dimethylsilylenebis [ 2-methyl-4- (3, 5-di-tert-butylphenyl) -7-methoxy-indenyl ] zirconium dichloride, which is first prealkylated with an alkylaluminum compound and then activated with a borate cocatalyst. The catalyst system is used for the preparation of polypropylene at temperatures between 30 ℃ and 70 ℃.

WO2011/135004 discloses complexes such as racemic dimethylsilylbis (2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl) zirconium dichloride as described in WO2007/116034 and prepared according to the emulsion/cure method as described in WO 2003/051934. These complexes are activated with aluminoxane cocatalysts and used for propylene polymerization.

WO 2012/075560 also describes a multistage (at least two stage) solution polymerization process for preparing ethylene copolymers wherein a phosphinimine catalyst and a cocatalyst comprising an alkylalumoxane and an ionic activator such as a boron compound are used.

None of the documents cited above mention the problem of effective comonomer insertion.

However, for an efficient process for the preparation of ethylene copolymers, it is important that the catalyst system used is specific for C used as comonomer_4-10Alpha-olefins have high activity.

From pair C_4-10Disadvantages caused by the low activity of the alpha-olefin comonomer are, for example, the increased amount of alpha-olefin comonomer required for introducing a certain amount of higher alpha-olefin comonomer units into the polymer and/or the removal of unreacted higher alpha-olefin from the polymer powder.

Another important and desirable property of the catalyst system employed is high productivity to produce the maximum amount of polyethylene with the smallest possible amount of catalyst.

Another point to note is that the high temperature solution process for olefin polymerization requires a thermally stable catalyst.

As described in WO 2003/102042, the solution process is characterized by a short residence time. Thus, in addition to having temperature stability, it is necessary for the catalyst systems used in these processes to be rapidly and fully activated. This is in sharp contrast to the requirements for catalysts used in slurry and gas phase processes, where residence time is longer and catalyst life is more important. Thus, catalysts that are valuable for slurry and gas phase processes may be poor choices for use in high temperature solution processes, and vice versa. As a solution to this problem, WO 2003/102042 suggests using organometallic complexes having a group 3 to 10 transition metal and a bridged indenoindolyl ligand in combination with an activator, preferably methylalumoxane.

Despite the considerable work that has been done in the field of metallocene catalysts, there remain problems relating to the productivity or activity of the catalyst system, especially when used in high temperature solution polymerization processes. It has been found that the productivity or activity is relatively low.

There is therefore still a need to find new catalyst systems for ethylene polymerization in high temperature solution polymerization processes, which are capable of producing ethylene copolymers with the desired properties and which have a high activity and/or productivity and a high reactivity towards the comonomers used in order to achieve high comonomer insertion and high thermal stability.

Accordingly, the present inventors have started to develop a new/improved catalyst system having better polymerization performance than the above polymerization catalyst system in terms of productivity, comonomer insertion and thermal stability.

The present inventors have now found an improved catalyst system which is capable of solving the above problems. In particular, the present invention combines a particular metallocene complex with an aluminoxane cocatalyst and optionally an additional boron-based cocatalyst for the preparation of ethylene copolymers in a high temperature solution polymerization process.

Disclosure of Invention

Viewed from one aspect, the present invention therefore relates to a catalyst system for the preparation of ethylene copolymers in a high temperature solution process, said catalyst system comprising

(i) Metallocene complexes of the formula (I)

Wherein

M is Hf or Zr,

x is a sigma ligand,

l is of the formula-SiR⁸ ₂A bridge of (a) wherein each R⁸Independently is C₁-C₂₀-hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀-aryl, C₇-C₂₀-aralkyl radical or C₇-C₂₀-an alkylaryl group,

n is 0,1 or 2,

R¹and R^1′Identical or capable of being different and can be linear or branched C₁-C₆-an alkyl group,

R²and R^2′Are identical or can be different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C₁-C₆-an alkyl group,

R⁵and R⁵' identical or different and can be H or straight-chain or branched C₁-C₆-an alkyl group OR an OR group, wherein R is C₁-C₆-alkyl radicals

R⁶And R^6′Identical or different and can be H or C (R)¹⁰)₃Group, wherein R¹⁰Are the same or different and R¹⁰Can be H or straight or branched C₁-C₆-an alkyl group,

or R⁵And R⁶And/or R^5′And R⁶' together form an unsubstituted 4-7 membered ring fused to the phenyl ring of the indenyl moiety, provided that if R is⁵And R⁶And R^5′And R⁶' together form an unsubstituted 5-membered ring fused to the phenyl ring of the indenyl moiety, then R²And R^2′Is other than C₁-an alkyl group,

and

R⁷and R^7′Can be identical or different and can be H or straight-chain or branched C₁-C₆-an alkyl group,

(ii) an aluminoxane cocatalyst, and

(iii) optionally a boron-containing promoter.

Viewed from a further aspect the present invention provides a novel class of metallocenes of formula (I) suitable for use in the present invention wherein

M is the component of Zr,

x is a Cl or methyl group,

l is of the formula-SiR⁸ ₂A bridge of (a) wherein two R are⁸Is the same C₁-C₄-a hydrocarbyl group or C₆-an aryl group,

R¹and R^1′Identical and are straight-chain or branched C₁-C₄-an alkyl group,

n is 1 or 2, and n is a hydrogen atom,

R²and R^2′Are the same and are CH₂-R⁹Group, wherein R⁹Is H or C₁-C₃-an alkyl group,

R⁵and R⁶Or R⁵' and R^6′Together form an unsubstituted 5-6 membered ring fused to the phenyl ring of the indenyl moiety,

and R is⁵And R⁶Or R⁵' and R⁶For R⁵Or R⁵' is an OR group, wherein R is C₁-C₄-an alkyl group, and for R⁶Or R⁶' is C (R)¹⁰)₃Group, wherein R¹⁰Are identical and R¹⁰Can be C₁-C₂-an alkyl group,

R⁷and R^7′Are all H.

Viewed from a further aspect the invention provides a process for the preparation of an ethylene copolymer, said process comprising contacting ethylene and C in the presence of a catalyst in a high temperature solution process at a temperature above 100 ℃_4-10An alpha-olefin comonomer polymerization, said catalyst comprising:

(i) the metallocene complexes of formula (I) as defined above,

(ii) an aluminoxane cocatalyst, and

(iii) optionally a boron-containing promoter.

Viewed from a further aspect the invention provides an ethylene copolymer prepared by a process as hereinbefore defined.

Detailed Description

Metallocene complexes

The single-site metallocene complexes, in particular the complexes defined by formula (I) specified in the present invention, used for the manufacture of ethylene copolymers are symmetrical or asymmetrical. By asymmetric complex it is meant that the two indenyl ligands forming the metallocene complex are different, i.e. each indenyl ligand bears a set of substituents which are chemically different or located at different positions relative to the other indenyl ligand. Rather, they are chiral, racemic bridged bis-indenyl metallocene complexes.

Although the complexes of the invention may be in their cis configuration, they are desirably in their trans configuration. For the purposes of the present invention, rac-trans means that the two indenyl ligands are oriented in opposite directions with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, while rac-cis means that the two indenyl ligands are oriented in the same direction with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the following figure.

Formula (I) is intended to encompass both the cis and trans configuration.

By their chemical nature, both trans and cis enantiomer pairs are formed during synthesis of the complex. However, by using the ligands of the present invention, it is simple to separate the preferred trans isomer from the cis isomer.

It is preferred that the metallocene complexes of the present invention are used as racemic trans isomers. Thus, desirably, at least 95 mole%, such as at least 98 mole%, especially at least 99 mole% of the metallocene catalyst is in the racemic trans-isomer form.

The invention can be carried out with metallocene complexes of the formula (I)

Wherein

M is Hf or Zr,

x is a sigma ligand,

n is 0,1 or 2,

R⁵and R⁵' identical or different and can be H or straight-chain or branched C₁-C₆-an alkyl group OR an OR group, wherein R is C₁-C₆-an alkyl group,

R⁶and R^6′Identical or different and can be H or C (R)¹⁰)₃Group, wherein R¹⁰Are the same or different and R¹⁰May be H or straight or branched C₁-C₆-an alkyl group,

or R⁵And R⁶And/or R^5′And R⁶' together form an unsubstituted 4-7 membered ring fused to the phenyl ring of the indenyl moiety, provided that if R is⁵And R⁶And R^5′And R⁶' together form an unsubstituted 5-membered ring fused to the phenyl ring of the indenyl moiety, then R²And R^2′Is other than C₁-an alkyl group;

and

R⁷and R^7′May be the same or different and may be H or straight or branched C₁-C₆-an alkyl group.

In formula (I), each X, which may be the same or different, is a sigma ligand, preferably a hydrogen atom, a halogen atom, R¹¹Radical, OR¹¹Radical, OSO₂CF₃Radical, OCOR¹¹Radical, SR¹¹Group, NR¹¹ ₂Group or PR¹¹ ₂Group, wherein R¹¹Is linear or branched, cyclic or acyclic C₁-C₂₀-alkyl radical, C₂-C₂₀-alkenyl radical, C₂-C₂₀-alkynyl radical, C₆-C₂₀-aryl radical, C₇-C₂₀An alkylaryl group or C₇-C₂₀-an aralkyl group; optionally containing heteroatoms belonging to groups 14 to 16, or SiR¹¹ ₃、SiHR¹¹ ₂Or SiH₂R¹¹。R¹¹Preferably C_1-6-an alkyl group, a phenyl group or a benzyl group, whereas the term halogen comprises a fluoro group, a chloro group, a bromo group and an iodo group, preferably a chloro group.

More preferably, each X is independently a hydrogen atom, a halogen atom, C_1-6-alkoxy groups or R¹¹Radicals, such as preferably C_1-6-an alkyl group, a phenyl group or a benzyl group.

Most preferably, X is a chloro or methyl group. Preferably both X groups are the same.

n is 0,1 or 2

R¹And R^1′May be straight or branched C₁-C₆Alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.

Preferably, R¹And R^1′Identical and are straight-chain or branched C₁-C₆-an alkyl group, preferably linear or branched C₂-C₆-an alkyl group, more preferably a linear or branched butyl group, and most preferably R¹And R^1′Is a tert-butyl group.

In a preferred embodiment, at least one of the phenyl groups is substituted with R¹Or R^1′So that n may be 0 only for one of the ligands, but not both.

If n is 1, then R¹And R^1′Preferably in the 4-position (para-position) of the phenyl ring, if n is 2, then R is¹And R^1′Preferably in the 3-and 5-positions of the phenyl ring.

For R¹And R^1′There may be different combinations:

both benzene rings are substituted by R¹And R^1′And n may be the same or different and is 1 or 2 for both phenyl rings.

Only one of the phenyl rings is substituted, wherein n is 1 or 2, preferably 1.

R²And R^2′Are identical or may be different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C₁-C₆Alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Preferably, R²And R^2′Are the same and are CH₂-R⁸Group, wherein R⁹Is H or straight or branched C₁-C₄-alkyl groups, more preferably, R²And R^2′Are the same and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C₁-C₃-alkyl groups, most preferably, R²And R^2′Both methyl groups or both isobutyl groups.

R⁵And R⁵' same or different and may be H or straight or branched C₁-C₆-alkyl groups OR OR groups, wherein R is a linear OR branched C₁-C₆-an alkyl group, and R⁶And R^6′Are the same or different and may be H or C (R)¹⁰)₃Group, wherein R¹⁰Are the same or different and R¹⁰May be H or straight or branched C₁-C₆-an alkyl group, or R⁵And R⁶And/or R^5′And R⁶' together form an unsubstituted 4-7, preferably 5-6, membered ring fused to the phenyl ring of the indenyl moiety, provided that if R is⁵And R⁶And R^5′And R⁶' together form an unsubstituted 5-membered ring fused to the phenyl ring of the indenyl moiety, then R²And R^2′Is other than C₁-an alkyl group.

If R is⁵And R⁶Or R⁵' and R^6′Together form an unsubstituted 4-7, preferably 5-6, membered ring fused to the phenyl ring of the indenyl moiety, then the substituent on the other indenyl moiety (R)⁵And R⁶Or R⁵' and R^6′) Preferably (for R)⁵Or R^5′) Is an OR group, wherein R is a linear OR branched C₁-C₆Alkyl groups (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl),preferably straight chain C₁-C₄-an alkyl group, more preferably C₁-C₂-alkyl groups and most preferably C₁-an alkyl group, and (for R)⁶Or R^6′) Is C (R)¹⁰)₃Group, wherein R¹⁰Are the same or different and R¹⁰May be H or straight or branched C₁-C₆-an alkyl group, preferably wherein R¹⁰Are the same or different and R¹⁰Is straight chain or branched C₁-C₄-an alkyl group, more preferably wherein R¹⁰Are identical and R¹⁰Is C₁-C₂-alkyl groups, most preferably C (R)¹⁰)₃The group is a tert-butyl group.

In one embodiment, R⁵And R⁶And R⁵' and R^6′Together form an unsubstituted 4-7, preferably 5-6, membered ring fused to the phenyl ring of the indenyl moiety. More preferably, R⁵And R⁶And R⁵' and R^6′Each forming an unsubstituted 5-membered ring fused to the phenyl ring of the indenyl moiety, provided that if R⁵And R⁶And R^5′And R⁶' together form an unsubstituted 5-membered ring fused to the phenyl ring of the indenyl moiety, then R²And R^2′Is other than C₁-an alkyl group.

Surprisingly, the inventors have found that if no additional boron promoter is used, where R is⁵And R⁶And R^5′And R⁶' both form an unsubstituted 5-membered ring fused to the phenyl ring of the indenyl moiety and R²And R^2′Is other than C₁The complexes of-alkyl groups likewise show very high comonomer insertion.

In another embodiment, it is also possible that, on both ligands, R⁵And R⁶And R^5′And R⁶' are both hydrogen.

Yet another possibility is that only one of the ligands is unsubstituted in positions 5 and 6.

R⁷And R^7′May be the same or differentAnd may be H or straight or branched C₁-C₆-alkyl radicals, preferably R⁷And R^7′Identical or different and may be H or straight or branched C₁-C₄-alkyl groups, more preferably, R⁷And R^7′Are the same or different and may be H or C₁-C₂-an alkyl group.

For preferred complexes, R⁷And R^7′Identical and are each H, or for other classes of preferred complexes, R⁷Or R^7′One of them is a straight chain or a branched chain C₁-C₆-an alkyl group, preferably linear or branched C₁-C₄-an alkyl group, more preferably C₁-C₂-an alkyl group and the other is H.

L is of the formula-SiR⁸ ₂A bridge of (a) wherein each R⁸Independently is C₁-C₂₀-hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀-aryl, C₇-C₂₀-aralkyl radical or C₇-C₂₀-an alkylaryl group.

Thus, the term C_1-20The hydrocarbon radical comprising C_1-20Alkyl radical, C_2-20Alkenyl radical, C_2-20Alkynyl, C_3-20Cycloalkyl radical, C_3-20Cycloalkenyl radical, C_6-20Aryl radical, C_7-20Alkylaryl group or C_7-20Aralkyl radicals or mixtures of these radicals, such as cycloalkyl substituted by alkyl.

Preferred C unless otherwise stated_1-20The hydrocarbon radical being C_1-20Alkyl radical, C_4-20Cycloalkyl radical, C_5-20Cycloalkyl-alkyl radical, C_7-20Alkylaryl group, C_7-20Aralkyl radical or C_6-20An aryl group.

Preferably, R⁸Are the same and are C₁-C₁₀-a hydrocarbyl group or C₆-C₁₀Aryl radicals, e.g. methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C_5-6-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, more preferably R⁸Are all C₁-C₄-a hydrocarbyl group or C₆-aryl group, most preferably R⁸Are all C₁-an alkyl group.

Particularly preferred complexes of the formula (I) are in their cis or trans configuration

Racemic dimethylsilylenebis [ 2-isobutyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-benzodiindan-1-yl ] zirconium dichloride or zirconium dimethyl,

racemic dimethylsilylene- [ eta⁵-6-tert-butyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-2-methylinden-1-yl]-[η⁵-4- (3, 5-di-tert-butylphenyl) -2-methyl-5, 6, 7-trihydro-s-benzodiindan-1-yl]Zirconium dichloride or dimethyl zirconium, and the zirconium chloride or dimethyl zirconium,

dimethylsilylenebis [ 2-methyl-4- (4' -tert-butylphenyl) -5,6, 7-trihydro-s-benzinden-1-yl ] zirconium dichloride or zirconium dimethyl,

dimethylsilylenebis [ 2-methyl-4- (3, 5-di-tert-butylphenyl) -5,6, 7-trihydro-s-benzinden-1-yl ] zirconium dichloride or zirconium dimethyl,

racemic dimethylsilyl [ (2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl) - (2-methyl-4-phenyl-inden-1-yl) ] zirconium dichloride or zirconium dimethyl.

For the purposes of the present invention, the terms dimethylsilyl, dimethylsilylene (dimethylsilylene) and dimethylsilylene (dimethylsilylene) are equivalent.

The metallocenes of formula (I) as described above comprise a new class of metallocenes which are suitable for use in the present invention, wherein in formula (I)

M is the component of Zr,

x is a Cl or methyl group,

n is 1 or 2, and n is a hydrogen atom,

and R is⁵And R⁶Or R⁵' and R⁶For R⁵Or R⁵' is an OR group, wherein R is C₁-C₄-an alkyl group, and for R⁶Or R⁶' is C (R)¹⁰)₃Group, wherein R¹⁰Are identical and R¹⁰Can be C₁-C₂-an alkyl group.

This new class of metallocenes is another embodiment of the present invention.

Synthesis of

The ligands required to form the catalysts of the invention can be synthesized by any method and skilled organic chemists can design various synthetic schemes for making the desired ligand materials. WO2007/116034 discloses the necessary chemistry and is incorporated herein by reference. Synthetic schemes are also commonly found in WO2002/02576, WO2011/135004, WO2012/084961, WO2012/001052 and WO 2011/076780.

Co-catalyst

To form the active catalyst species, it is often necessary to employ a cocatalyst as is well known in the art. The present invention requires the use of an aluminoxane cocatalyst and optionally an additional boron-containing cocatalyst.

The aluminoxane cocatalyst can be one of the formulae (II):

wherein n is generally from 6 to 20 and R has the following meaning.

Aluminoxanes are formed by partial hydrolysis of an organoaluminum compound, such as an organoaluminum compound of the formula AlR₃、AlR₂Y andAl₂R₃Y₃wherein R may be, for example, C1-C10 alkyl (preferably C1-C5 alkyl), or C3-10-cycloalkyl, C7-C12-aralkyl or alkaryl and/or phenyl or naphthyl, and wherein Y may be hydrogen, halogen (preferably chlorine or bromine) or C1-C10 alkoxy, preferably methoxy or ethoxy. The oxygen-containing aluminoxanes produced are generally not pure compounds but mixtures of oligomers of the formula (I).

The preferred aluminoxane in the process according to the invention is Methylaluminoxane (MAO). Since the alumoxanes used as cocatalysts according to the present invention are not pure compounds due to their mode of preparation, the molar concentrations of the alumoxane solutions hereinafter are based on their aluminum content.

However, it has surprisingly been found that in the case of heterogeneous catalysis, in which the catalyst is not supported on any external support or as described above, a higher activity can be obtained in the specific case if a boron-based cocatalyst is also employed as cocatalyst. It will be appreciated by those skilled in the art that in the case of boron-based cocatalysts, the complex is typically preactivated by reaction with an alkyl aluminum compound (e.g., TIBA). This process is well known and any suitable aluminum alkyl may be used, preferably AlR of formula (VIII)₃Wherein R is a linear or branched C₂-C₈-an alkyl group.

Preferred alkyl aluminum compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum and triisooctylaluminum.

The present invention preferably comprises the use of a boron cocatalyst with the aluminoxane rather than these simple aluminum alkyls in combination with a boron cocatalyst.

The boron-based cocatalysts of interest comprise a catalyst comprising borate 3⁺Ionic boron compounds, i.e. borate compounds. These compounds generally contain an anion of the formula:

(Z)₄B^-(III)

wherein Z is an optionally substituted phenyl derivative, said substituent being halogen-C_1-6-alkyl radicalsOr a halogen group. A preferred choice is fluoro or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

Such ionic cocatalysts preferably contain a non-coordinating anion, such as tetrakis (pentafluorophenyl) borate.

Suitable counterions are protonated amine or aniline derivatives or phosphonium ions. These counterions can have the general formula (IV) or (V):

NQ₄ ⁺(IV) or PQ₄ ⁺(V)

Wherein Q is independently hydrogen, C_1-6Alkyl radical, C_3-8Cycloalkyl, phenyl C_1-6-alkylene-or optionally substituted Ph. Optional substituents may be C1-6-alkyl, halogen or nitro. There may be one or more than one such substituent. Preferred substituted Ph groups therefore include para-substituted phenyl, preferably tolyl or dimethylphenyl.

It is preferred that at least one Q group is hydrogen, and therefore preferred compounds are those of the formula:

NHQ₃ ⁺(VI) or PHQ₃ ⁺(VII)

Preferred phenyl radicals-C_1-6-the alkyl-group comprises a benzyl group.

Suitable counterions therefore include: methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylphenylammonium, diphenylammonium, N-dimethylanilinium, trimethylammonium, triethylammonium, tri-N-butylammonium, methyldiphenylammonium, p-Br-N, N-dimethylanilinium or p-nitro-N, N-dimethylanilinium, in particular dimethylammonium or N, N-dimethylanilinium. The use of pyridinium as the ion is another option.

Phosphonium ions of interest include triphenylphosphonium, triethylphosphonium, diphenylphosphonium, tris (methylphenyl) phosphonium and tris (dimethylphenyl) phosphonium.

A more preferred counterion is trityl (CPh)₃ ⁺) Or an analogue thereof, wherein the Ph group is functionalised to carry more than one alkyl group. Thus, highly preferred borate salts for use in the present invention include tetrakis (pentafluorophenyl) borate ion.

Preferred ionic compounds that may be used according to the invention comprise: tributylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (trifluoromethylphenyl) borate, tributylammonium tetrakis (4-fluorophenyl) borate, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-dipropylammonium tetrakis (pentafluorophenyl) borate, di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, or ferrocenium tetrakis (pentafluorophenyl) borate.

Preference is given to triphenylcarbenium tetrakis (pentafluorophenyl) borate, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

It has been surprisingly found that certain boron promoters are particularly preferred. Preferred borates for use in the invention therefore include the trityl ion. The use of N, N-dimethylammonium tetrakis (pentafluorophenyl) borate and Ph is therefore particularly preferred₃CB(PhF₅)₄And the like.

In one embodiment, preferably a cocatalyst, an aluminoxane catalyst and a boron-based cocatalyst are used in the catalyst system of the present invention.

In another embodiment, if a complex is used, wherein R is⁵And R⁶And R^5′And R^6′Both forming an unsubstituted 5-membered ring fused to the benzene ring of the indenyl moiety, it is also preferred to use only aluminoxane as a cocatalyst.

AlR of the formula (VIII) in amounts known to the person skilled in the art may also be added₃Wherein R is a linear or branched C₂-C₈-an alkyl group as acid scavenger.

Suitable amounts of cocatalyst will be known to those skilled in the art.

The ratio of boron to the metallocene ion may be in the range of from 0.5:1 to 10:1 moles/mole, preferably from 1:1 to 10:1, especially from 1:1 to 5:1 moles/mole.

The molar ratio of Al in the aluminoxane to the metal ion of the metallocene may be in the range of 1:1 to 2000:1 moles/mole, preferably 10:1 to 1000:1, more preferably 50:1 to 500:1 moles/mole.

Catalyst manufacture

The metallocene complexes of the invention are used in combination with cocatalysts for the polymerization of ethylene with C in high temperature solution polymerization processes_4-10Catalyst system for the polymerization of alpha-olefin comonomers.

The catalyst system of the present invention can be used in unsupported form or in solid form. The catalyst system of the present invention can be used as a homogeneous catalyst or a heterogeneous catalyst.

The catalyst system of the invention in solid form, preferably in solid particulate form, does not contain an external support, but is still in solid form.

By free of an external support is meant that the catalyst does not contain an external support material, such as an inorganic support material (e.g., silica or alumina) or an organic polymeric support material.

a) No load

Unsupported catalyst systems suitable for use in the present invention can be prepared in solution, for example in an aromatic solvent such as toluene, by contacting the metallocene (as a solid or as a solution) with a cocatalyst such as methylaluminoxane and/or borane or borate, which is previously in an aromatic solvent, or can be prepared by sequential addition of the dissolved catalyst components to the polymerization medium.

b) Solid forms

In an alternative embodiment, in order to provide the catalyst of the invention in solid form without the use of an external carrier, it is preferred to use a liquid/liquid emulsion system. The process comprises forming dispersed catalyst components (i) (complex) and (ii) + optionally (iii) (co-catalyst) in a solvent and solidifying the dispersed droplets to form solid particles.

In this case, if alumoxane is used together with the boron-based cocatalyst, it is particularly preferred to contact the alumoxane with the metallocene before the borate is added. Both cocatalyst components and the metallocene are preferably present in one solution.

In particular, the process comprises preparing a solution of the catalyst component; dispersing the solution in a solvent to form an emulsion, wherein the one or more catalyst components are present in droplets of the dispersed phase; immobilizing the catalyst component in dispersed droplets in the absence of an external particulate porous support to form solid particles comprising the catalyst, and optionally recovering the particles.

The process enables the manufacture of active catalyst particles having an improved morphology (e.g. having a predetermined particle size, spherical shape, dense structure, excellent surface properties) without the use of any external porous support material, such as an inorganic oxide, such as silica. The catalyst particles may have a smooth surface, they may be compact in nature and the catalyst active components may be uniformly distributed throughout the catalyst particles.

A full disclosure of the required method steps can be found in WO03/051934, which is incorporated herein by reference.

All or a portion of the preparation steps may be accomplished in a continuous manner. Reference is made to WO2006/069733, which describes the principle of such a continuous or semi-continuous preparation method of solid catalyst types prepared via an emulsion/solidification method.

The catalysts formed preferably have good stability/kinetics in terms of reaction life, high activity and the catalysts enable low ash contents.

The use of heterogeneous, unsupported catalysts (i.e. "self-supported" catalysts) can have the disadvantage of being somewhat soluble in the polymerization medium, i.e. during slurry polymerization, some of the active catalyst components can leach out of the catalyst particles, thereby possibly losing the original good catalyst morphology. These leached catalyst components are very active and can cause problems during polymerization. Thus, the amount of leached components should be minimized, i.e. all catalyst components should be kept in heterogeneous form.

Furthermore, due to the high content of catalytically active species in the catalyst system, high temperatures are generated from the supported catalyst at the start of the polymerization, which can lead to melting of the product material. Both of these effects, i.e., partial dissolution and heating of the catalyst system, can lead to fouling, sheeting and deterioration of the morphology of the polymeric material.

To minimize possible problems associated with high activity or leaching, it is preferred to "pre-polymerize" the catalyst prior to using the catalyst in the polymerization process. It is to be noted in this connection that the prepolymerization is part of the catalyst preparation process and is a step carried out after the formation of the solid catalyst. The catalyst pre-polymerization step is not part of the actual polymerization configuration and may also include a pre-polymerization step of conventional processes. After the catalyst prepolymerization step, a solid catalyst is obtained and used in the polymerization.

The catalyst "prepolymerization" occurs after the curing step of the aforementioned liquid-liquid emulsification process. The prepolymerization can be carried out by known methods described in the art, such as described in WO 2010/052263, WO 2010/052260 or WO 2010/052264. Preferred embodiments of this aspect of the invention are as described herein.

The use of a catalyst pre-polymerisation step provides the advantage of minimising leaching of the catalyst components and hence local overheating.

Polymer and method of making same

The polymers to be prepared using the catalyst system of the invention are ethylene and C_4-10Copolymers of alpha-olefin comonomers such as 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc. Preferably butene, hexene or octene and more preferably octene is used as comonomer.

The comonomer content in the polymer may be up to 40 wt%, preferably between 5 and 40 wt%, more preferably between 10 and 38 wt%, and more preferably between 15 and 36 wt%.

The density of the polymer (measured according to ISO 1183-187) was 0.850g/cm³To 0.950g/cm³In the range, preferably 0.850g/cm³To 0.945g/cm³In the range of, and more preferably 0.850g/cm³To 0.940g/cm³Within the range.

The Mw/Mn values of the polymers of the present invention are less than 5, such as in the range of 2.0 to 4.5.

The melting point of the polymer to be prepared (measured by DSC according to ISO 11357-3: 1999) is below 130 ℃, preferably below 120 ℃, more preferably below 110 ℃ and most preferably below 100 ℃.

Polymerisation

The ethylene copolymers defined above are prepared by high temperature solution polymerization at temperatures above 100 ℃ using the catalyst system of the present invention.

In view of the present invention, the process is essentially based on polymerizing monomers and suitable comonomers in a liquid hydrocarbon solvent, wherein the resulting polymer is soluble. The polymerization is carried out at a temperature higher than the melting point of the polymer, as a result of which a polymer solution is obtained. The solution is flashed to separate the polymer from unreacted monomer and solvent. The solvent is then recovered and reused in the process.

Solution polymerization processes (as compared to gas phase or slurry processes) are distinguished by their short reactor residence times, thus allowing very fast brand transitions and significant flexibility in producing a wide range of products in a short production cycle.

According to the present invention, the solution polymerization process used is a high temperature solution polymerization process employing a polymerization temperature above 100 ℃. Preferably, the polymerization temperature is at least 110 ℃, more preferably at least 150 ℃. The polymerization temperature may be up to 250 ℃.

The pressure in the solution polymerization process used according to the present invention is preferably in the range of from 10 to 100 bar, preferably from 15 to 100 bar, and more preferably from 20 to 100 bar.

The liquid hydrocarbon solvent used is preferably one which may be unsubstituted or substituted by C_1-4Alkyl radical substituted C_5-12Hydrocarbons, such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha. More preferably unsubstituted C_6-10-a hydrocarbon solvent.

A known solution technique suitable for use in the method according to the invention is the COMPACT technique.

Advantages of

The novel catalyst system comprising component (i), component (ii) and optionally component (iii) can advantageously be used for ethylene copolymerization in high temperature solution polymerization processes.

The catalyst system according to the present invention shows excellent productivity, excellent comonomer insertion and thermal stability if used for ethylene copolymerization in a high temperature solution polymerization process.

Applications of

The polymers prepared by the catalyst system of the present invention are useful in all kinds of end articles such as pipes, films (cast films, blown films), fibers, molded articles (such as injection molded articles, blow molded articles, rotomolded articles), extrusion coatings, and the like.

The invention will now be illustrated with reference to the following non-limiting examples.

Example (b):

method of producing a composite material

Determination of Al and Zr (ICP-method)

Elemental analysis of the catalyst was performed using a solid sample of mass m. The catalyst was deactivated by replacing the inert storage conditions with ambient air, first inertly through the needle and actively by applying three vacuums to the sampling vessel. Fresh deionized water (5% of V) and nitric acid (HNO) were added simultaneously by first cooling on dry ice₃65%, 5% of V) the sample is dissolved to volume V. The sample was transferred in its entirety to the volumetric flask with deionized water and the sampling vessel was rinsed. Hydrofluoric acid (HF, 40%, 3% of V) was added to the volumetric flask and the volume V was obtained by adding fresh deionized water. The prepared sample solution was kept stable for two hours.

Analysis was performed at room temperature using a Thermo element iCAP 6300 inductively coupled plasma-optical emission spectrometer (ICP-OES) calibrated using the following: blank (5% HNO3, 5% HF in deionized water solution), and 6 standards of 0.5ppm, 1ppm, 10ppm, 50ppm, 100ppm, and 300ppm Al, and 0.5ppm, 1ppm, 5ppm, 20ppm, 50ppm, and 100ppm B and P in 5% HNO3, 3% HF in deionized water solution.

Just prior to analysis, a "slope reset" calibration was performed using a blank and 100ppm Al, 50ppm B, P standards, and quality control samples (5% HNO3, 20ppm Al, 5ppm B, P in a solution of 3% HF in DI water) were run to confirm the slope reset. QC samples were also run after every 5 th sample and at the end of the planned analysis group.

The reported values are the average of three consecutive aliquots taken from the same sample and are correlated back to the original catalyst by inputting the original mass m and dilution volume V of the sample into the software.

DSC analysis

Melting point (T) was determined on a DSC200TA instrument by the following procedure_m) And crystallization temperature (T)_c): a5-7 mg sample of the polymer was placed in a closed DSC aluminum pan, the sample was heated at 10 ℃/min from-30 ℃ to 180 ℃, held at 180 ℃ for 5 minutes, cooled from 180 ℃ to-30 ℃, held at-30 ℃ for 5 minutes, and heated at 10 ℃/min from-30 ℃ to 180 ℃. Reported T_mIs the maximum value of the curve of the second heating sweep and T_cThe maximum of the curve for the cooling scan.

Quantification of comonomer content by NMR spectroscopy

Quantitative Nuclear Magnetic Resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymer.

Quantification of¹³C{¹H } NMR spectra were used in the melt-state¹H and¹³c records from Bruker Advance III 500NMR spectrometers operating at 500.13 and 125.76MHz respectively. Use of nitrogen at 150 ℃ for all pneumatic units¹³A C-optimized 7mm Magic Angle Spinning (MAS) probe recorded all spectra. Approximately 200mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setting was chosen primarily for the high sensitivity required for rapid identification and accurate quantification { klimke06, parkinson07, cartignoles 09, parkinson11 }. Standard single pulse excitation was applied with transient NOEs at 3s short cycle delay pollard04, klimke06 and RS-HEPT decoupling scheme fililip 05, griffin 07. A total of 1024(1k) transients were obtained for each spectrum. This setting was chosen because of its high sensitivity to low comonomer content quantification.

For quantitative determination¹³C{¹H NMR spectra were processed, integrated and quantitative properties determined using a custom spectral analysis automation program. All chemical shifts are internally referenced to the bulk methylene signal at 30.00ppm (⁺){randall89}。

Characteristic signals corresponding to the inserted 1-octene were observed (randall89, liu01, qiu07) and all comonomer contents were calculated with respect to all other monomers present in the polymer.

Characteristic signals resulting from isolated 1-octene insertions (i.e., EEOEE comonomer sequences) were observed. Isolated 1-octene insertions were quantified using integration of the signal at 38.32 ppm. The integrals were assigned to the unresolved signals corresponding to the a B6 and a B6B6 sites of the isolated (EEOEE) 1-octene sequence and the isolated doubly discontinuous (EEOEE) 1-octene sequence, respectively. To compensate for the effect of two abb B6B6 sites, the integral at 24.7ppm of β β B6B6 site was used:

O＝I_*B6+*βB6B6-2*I_ββB6B6

characteristic signals resulting from consecutive 1-octene insertions (i.e., EEOOEE comonomer sequences) were also observed. This successive 1-octene insertion was quantified using the integral of the signal at 40.48ppm assigned to the α α B6B6 site over the number of reported sites per comonomer:

OO＝2*I_ααB6B6

characteristic signals resulting from isolated non-continuous 1-octene insertions (i.e., eeoeoeoe comonomer sequences) were also observed. This isolated non-contiguous 1-octene insertion was quantified using the integral of the signal at 24.7ppm assigned to β β β B6B6 site over the number of sites reported per comonomer:

OEO＝2*I_ββB6B6

characteristic signals resulting from isolated triple-continuous 1-octene insertions (i.e., EEOOOEE comonomer sequences) were also observed. This isolated triple continuous 1-octene insertion was quantified using the integration of the signal at 41.2ppm assigned to the α α γ B6B6 site over the number of reported sites per comonomer:

OOO＝3/2*I_ααγB6B6B6

no other symbolic signal for other comonomer sequences was observed, the total 1-octene comonomer content was calculated based on the amount of isolated (EEOEE) 1-octene comonomer sequence, isolated doubly continuous (EEOOEE) 1-octene comonomer sequence, isolated discontinuous (eeoeoe) 1-octene comonomer sequence and isolated triply continuous (EEOOOEE) 1-octene comonomer sequence only:

O_{general assembly}＝O+OO+OEO+OOO

Characteristic signals resulting from saturated end groups were observed. The saturated end groups were quantified by the average integration of the two resolved signals at 22.84 and 32.23 ppm. The 22.84ppm integral is attributed to the unresolved signals corresponding to the 2B6 and 2S sites of 1-octene and saturated chain ends, respectively. The 32.23ppm integral is attributed to the unresolved signals corresponding to the 3B6 and 3S sites of 1-octene and saturated chain ends, respectively. To compensate for the effect of 2B6 and 3B 61-octene sites, the total 1-octene content was used:

S＝(1/2)*(I_2S+2B6+I_3S+3B6-2*O_{general assembly})

Ethylene comonomer content was quantified by integration of the bulk methylene (bulk) signal at 30.00 ppm. The integral contains the gamma and 4B6 sites from 1-octene and⁺a site. The total ethylene comonomer content was calculated based on bulk integration and compensation for observed 1-octene sequences and end groups:

E_{general assembly}＝(1/2)*[I_{Main body}+2*O+1*OO+3*OEO+0*OOO+3*S]

It is noted that there is no need for compensation of bulk integration for isolated triple insertion (EEOOOEE) 1-octene sequences present, since the number of under-and over-calculated ethylene units is equal.

The total mole fraction of 1-octene in the polymer is then calculated as:

fO＝(O_{general assembly}/(E_{General assembly}+O_{General assembly})

Total comonomer insertion of 1-octene in weight percent calculated from the mole fraction in standard manner:

o [ wt% ] ═ 100 (fO 112.21)/((fO 112.21) + ((1-fO) × 28.05))

klimke06

Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006；207:382.

parkinson07

Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007；208:2128.

parkinson11

NMR spectra of Polymers Innovative spectra for Complex macromolecules, Chapter 24, 401(2011)

pollard04

Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004；37:813.

filip05

Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239

griffin07

Griffin,J.M.,Tripon,C.,Samoson,A.,Filip,C.,and Brown,S.P.,Mag.Res.inChem.200745,S1,S198

castignolles09

Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer50(2009)2373

zhou07

Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225

busico07

Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128

randall89

J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201.

qui07

Qiu,X.,Redwine,D.,Gobbi,G.,Nuamthanom,A.,Rinaldi,P.,Macromolecules2007,40,6879

liu01

Liu,W.,Rinaldi,P.,McIntosh,L.,Quirk,P.,Macromolecules 2001,34,4757

GPC: average molecular weight, molecular weight distribution, and polydispersity index (Mn, Mw/Mn)

Molecular weight averages (Mw, Mn), Molecular Weight Distributions (MWD) described by polydispersity index PDI ═ Mw/Mn (where Mn is the number average molecular weight and Mw is the weight average molecular weight), and their breadth were determined by Gel Permeation Chromatography (GPC) according to ISO 16014-4:2003 and ASTM D6474-99. A Waters GPCV2000 instrument equipped with a differential refractive index detector and an online viscometer was used with 2 XGMHXL-HT and 1 XG 7000HXL-HT TSK-gel columns from Tosoh Bioscience and 1,2, 4-trichlorobenzene (TCB, stabilized with 250mg/L2, 6-di-tert-butyl-4-methyl-phenol) as solvent at 140 ℃ and at a constant flow rate of 1 mL/min. 209.5. mu.L of sample solution was injected for each analysis. The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with at least 15 narrow MWD Polystyrene (PS) standards in the range of 1kg/mol to 12000 kg/mol. Mark Houwink constants for the PS, PE and PP used were according to ASTM D6474-99. All samples were prepared by: 0.5-4.0mg of polymer was dissolved in 4mL (at 140 ℃) of stabilized TCB (same as mobile phase) and kept at maximum 160 ℃ for up to 3 hours under continuous gentle shaking before introduction into the GPC instrument.

Chemical product

MAO was purchased from Chemtura and used as a 30 wt% solution in toluene.

Triphenylcarbenium tetrakis (pentafluorophenyl) borate (alternatively known by the name trityl tetrakis (pentafluorophenyl) borate) (CAS136040-19-2) is purchased from Acros (tritylBF 20).

1-octene (99%, Sigma Aldrich) as a comonomer was dried over molecular sieves and degassed with nitrogen before use.

Heptane and decane (99%, Sigma Aldrich) were dried over molecular sieves and degassed with nitrogen before use.

Example (b):

for the purposes of the present invention, the terms dimethylsilyl, dimethylsilylene and dimethylsilylene are equivalent.

Preparation of the Complex

1. Complex 1-Zr: preparation of trans-dimethylsilylene (2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl) (2-methyl-4- (4-tert-butyl-phenyl) indenyl) zirconium dichloride (C1-Zr) as described in patent application WO2013/007650A1

2. Complex 2-Zr: racemic dimethylsilyl (2-methyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-6-tert-butylinden-1-yl) - (2-methyl-4- (3, 5-di-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-benzodiindan-1-yl zirconium dichloride (C2-Zr) was prepared as follows:

general procedure for C2-Zr

Such as in [ Stork, g.; white, w.n.j.am.chem.soc.1956,78,4604.]1-tert-butyl-2-methoxybenzene was synthesized by alkylation of 2-tert-butylphenol (Acros) with dimethyl sulfate (Merck) in the presence of aqueous NaOH (Reachim, Russia). 2-methyl-4-bromo-5-methoxy-6-tert-butyl indanone was prepared as described in WO 2013007650. As in [ hindermann, l.beilstein j.org.chem.2007,3,1, respectively.]And [ Matsubara, k.; ueno, k.; shibata, y. organometallics 2006,25,3422.]Synthesis of bis (2, 6-diisopropylphenyl) imidazolium chloride (i.e., IPr (HCl)) and (IPr) NiCl as described in (1)₂(PPh₃). Anisole (Acros), 3-methylanisole (Acros), tert-butyltoluene (Aldrich), P₄O₁₀(Reachim)、Pd(P^tBu₃)₂(Strem), 1.0MZnCl in THF₂(Aldrich), 1.0M 3, 5-di-tert-butylphenyl magnesium bromide in THF (Aldrich), hexane (Reachim, Russia), N-bromosuccinimide (Acros), dry ethanol (Merck), diethyl methylmalonate (Aldrich), methyl iodide (Acros), acetone (Reachim, Russia), tetraethylammonium iodide (Acros), 1-bromo-4-tert-butylbenzene (Acros), CuCN (Merck), methanesulfonic acid (Aldrich), sodium tetraphenylborate (Aldrich), palladium acetate (Aldrich), copper cyanide (Merck), lithium aluminum hydride (Aldrich), bromobenzene (Acros), 2.5M in hexane (Aldrich)ⁿBuLi(Chemetall)、ZrCl₄(THF)₂(Aldrich)、NaBH₄(Aldrich)、Ni(OAc)₂(Aldrich), silica gel 60(40-63um, Merck), AlCl₃(Merck), bromine (Merck), benzoyl peroxide (Aldrich), iodine (Merck), NaHCO₃(Merck)、Na₂CO₃(Merck)、K₂CO₃(Merck)、Na₂SO₄(Merck)、Na₂SO₃(Merck), sodium metal (Merck), thionyl chloride (Merck), magnesium turnings (Acros), sodium acetate, trihydrate (Merck), tetraethylammonium iodide (Acros), triphenylphosphine (Acros), KOH (Merck), Na₂SO₄(Akzo Nobel), TsOH (Aldrich), 12M HCl (Reachim, Russia), methanol (Merck), absolute ethanol (Merck), CDCl₃And DMSO-d₆(Deutero GmbH) and hexane (Merck), carbon tetrachloride (Merck), ether (Merck), ethyl acetate (Merck), toluene (Merck) and CH for extraction₂Cl₂(Merck) was used as it is. Tetrahydrofuran (Merck), ether (Merck) and dimethoxyethane (Acros) freshly distilled from the benzophenone ketyl group were used. Dichloromethane (Merck) for organometallic Synthesis and CD for NMR experiments₂Cl₂CaH for (Deutero GmbH)₂Drying and maintaining. Toluene (Merck), n-octane (Merck), and hexane (Merck) for organometallic synthesis were held with Na/K alloy and distilled. Dichlorodimethylsilane (Merck) and methacrylic acid (Acros) were distilled prior to use.

A) 6-tert-butyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-2-methylindan-1-one

30.7g (98.6mmol) of 2-methyl-4-bromo-5-methoxy-6-tetrabutylindanone, 30.6g (128mmol) of 3, 5-di-tert-butylphenyl boronic acid, 29.7g (280mmol) of Na₂CO₃1.35g (5.92 mmol; mol%) Pd (OAc)₂3.15g (11.8 mmol; 12 mol%) PPh₃A mixture of 130ml of water and 380ml of 1, 2-dimethoxyethane was refluxed for 12 h. After this time, the reaction mixture was quenched with water and the solvent was evaporated. The residue was dissolved in 500ml of dichloromethane and the solution was washed with 500ml of water. The organic layer was separated and the aqueous layer was extracted with another 100ml of dichloromethane. The combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The crude product separated from the residue using flash chromatography on silica gel 60(40-63um, hexane-dichloromethane ═ 2:1 vol) was then recrystallized from n-hexaneCrystallized to yield 18.5g (43%) of a white solid.

For C₂₉H₄₀O₂The analytical calculation of (2): c, 82.81; h, 9.59. Measurement: c, 83.04; h, 9.75.

¹H NMR(CDCl₃) 7.74(s,1H, 7-H in indan-1-one), 7.41(t, J ═ 1.6Hz,1H, C₆H₃ ^tBu₂4-H) of (1), 7.24(d, J ═ 1.6Hz, C₆H₃ ^tBu₂2,6-H as in (1), 3.24(s,3H, OMe),3.17(dd, J ═ 17.3Hz, J ═ 8.0Hz,1H, 3-H as in indan-1-one), 2.64(m,1H, 2-H as in indan-1-one), 2.47(dd, J ═ 17.3Hz, J ═ 3.7Hz,1H, 3-H' as in indan-1-one), 1.43(s,9H, 6 as in indan-1-one)^tBu),1.36(s,18H,C₆H₃ ^tBu₂In (1)^tBu),1.25(d, J ═ 7.3Hz,3H, 2-Me in indan-1-one).

2, b) 2-methyl-5-tert-butyl-6-methoxy-7- (3, 5-di-tert-butylphenyl) -1H-indene

To a solution of 16.3g (38.8mmol) 2-methyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-6-tert-butyl-indan-1-one in 200ml THF cooled to 5 deg.C was added 1.47g (38.9mmol) NaBH₄. Thereafter, 80ml of methanol was added dropwise to the mixture at 5 ℃ over about 7 hours by vigorous stirring. The resulting mixture was evaporated to dryness and the residue was treated with 300ml dichloromethane and 300ml 2M HCl. The organic layer was separated and the aqueous layer was extracted with another 100ml of dichloromethane. The combined organic extracts were evaporated to dryness to give a colorless oil. To a solution of this oil in 250ml of toluene was added 0.1g of TsOH, and the mixture was refluxed with dean-Stark head for 15min and then cooled to room temperature using a water bath. The resulting solution was treated with 10% Na₂CO₃And (4) washing with an aqueous solution. The organic layer was separated and the aqueous layer was extracted with 2x 50ml dichloromethane. The combined organic extracts are washed with water₂CO₃Dried and then passed through a short layer of silica gel 60(40-63 μm). The silica gel layer was additionally washed with 100ml dichloromethane. The combined organic effluents are evaporated to dryness to give 15.7g (99%) of a white crystalline product, which was further used without additional purification.

For C₂₉H₄₀Analytical calculation of O: c, 86.08; h, 9.96. Measurement: c, 86.26; h, 10.21.

¹H NMR(CDCl₃):7.36(t,J＝1.8Hz,1H,C₆H₃ ^tBu₂4H of (1), 7.33(d, J ═ 1.8Hz,2H, C)₆H₃ ^tBu₂2,6-H in (s,1H, 4-H in indenyl), 6.21 (s,1H, 3-H in indenyl), 3.17(s,3H, OMe),3.14(s,2H, 1-H in indenyl), 2.06(s,3H, 2-Me in indenyl), 1.44(s,9H, 5 in indenyl)^tBu),1.35(s,18H,C₆H₃ ^tBu₂In (1)^tBu)。¹³C{¹H}NMR(CDCl₃) 150.4,145.2 (two resonance states), 141.7,140.9,140.6,137.3,132.5,126.9,124.0,120.1,116.9,60.2,43.0,35.2,34.9,31.5,31.0, 16.7.

2, c) 2-methyl-3, 5,6, 7-tetrahydro-s-benzodiindene-1 (2H) -one

242g (1.05mol) of 2-bromo-2-methylpropanoyl bromide are added dropwise to 333g (2.5mol) of AlCl in 15min₃In 900ml of a suspension in dichloromethane cooled to-30 ℃. The resulting mixture was stirred for 15min, then 118g (1.0mol) of indane were added at the same temperature. Then, the cooling bath was removed and the solution was stirred at room temperature overnight. The reaction mixture was poured into 2kg of crushed ice, the organic phase was separated and the aqueous phase was extracted with 3x 500ml of dichloromethane. The combined organic extracts are washed with water₂CO₃Washing with aqueous solution, using K₂CO₃Dried and passed through a short pad of silica gel 60(40-63 μm). The effluent was evaporated to dryness to yield a yellow oil. The oil was distilled in vacuo to yield 145g (78%) of a slightly yellowish oil, b.p.120-140 deg.C/5 mmHg. The 2-methyl-3, 5,6, 7-tetrahydro-s-benzinden-1 (2H) -one thus obtained contaminated with about 15% of the angular isomer, i.e.2-methyl-1, 6,7, 8-tetrahydro-as-benzinden-3 (2H) -one, is allowed to stand without further purificationThe application is as follows.

For C₁₃H₁₄Analytical calculation of O: c, 83.83; h, 7.58. Measurement: c, 83.74; h, 7.39.

¹H NMR(CDCl₃):7.54(s,1H,8-H),7.24(s,1H,4-H),3.30(dd,J＝16.6Hz,J＝7.3Hz,1H,3-CHH’),2.84-3.00(m,4H,5-CH₂And 7-CH₂),2.63-2.74(m,1H,2-H),2.63(dd,J＝16.6Hz,J＝3.6Hz,1H,3-CHH’),2.10(tt,2H,6-CH₂),1.28(d,J＝7.4Hz,3H,2-Me)。¹³C{¹H}NMR(CDCl₃):208.84,152.87,152.50,144.05,135.06,121.94,119.10,42.36,34.65,33.01,31.95,25.70,16.40。

D)4, 8-dibromo-2-methyl-3, 5,6, 7-tetrahydro-s-benzodiindene-1 (2H) -one

A solution of 141.7g (760.8mmol) 2-methyl-3, 5,6, 7-tetrahydro-s-benzinden-1 (2H) -one (prepared as described above, containing about 15% of the goniomer) in 430ml dichloromethane was added dropwise at-10 ℃ to 260g (1.95mol, 2.56 equivalents) AlCl over 0.5H₃In a suspension in 700ml of dichloromethane. The reaction mixture was stirred at this temperature for 10min, then 1.3g of iron powder was added. Thereafter, 250g (1.56mol, 2.06 eq) of bromine were added dropwise over 1 hour. The resulting mixture was stirred at room temperature overnight and then poured onto a bottle of 2000cm³And crushing the ice. Separating the organic layer; the aqueous layer was extracted with 3 × 300ml dichloromethane. The combined organic extracts are washed with water₂CO₃Washing with aqueous solution, using K₂CO₃Dried, passed through a short pad of silica gel 60(40-63 μm) and then evaporated to dryness. The crude product (about 264g) was recrystallized from 3000ml hot n-hexane to give the title product in about 95% purity. The material was further recrystallized from 2400ml of hot n-hexane. This procedure yielded 117g of 4, 8-dibromo-2-methyl-3, 5,6, 7-tetrahydro-s-benzodiindan-1 (2H) -one. The mother liquor was evaporated to dryness and a further portion of the title product was isolated from the residue by flash chromatography on silica gel 60(40-63 μm). This procedure yielded 109g of 4, 8-dibromo-2-methyl-3, 5,6, 7-tetrahydro-s-benzeneAnd of the benzodiindan-1 (2H) -one and 29.2g of the angular isomeric product, i.e. 4, 5-dibromo-2-methyl-1, 6,7, 8-tetrahydro-as-benzinden-3 (2H) -one. Thus, the total yield of the title product was 226g (87%).

4, 8-dibromo-2-methyl-3, 5,6, 7-tetrahydro-s-benzodiindan-1 (2H) -one.

For C₁₃H₁₂Br₂Analytical calculation of O: c, 45.38; h, 3.52. Measurement: c, 45.64; h, 3.60.

¹H NMR(CDCl₃):3.23(dd,J＝17.6Hz,J＝8.0Hz,1H,3-CHH’),3.04-3.12(m,4H,5-CH₂And 7-CH₂) 2.76(m,1H,2-H),2.54(dd, J ═ 17.6Hz, J ═ 3.7Hz,1H, 3-CHH'), 2.18 (quintuple, 2H, 6-CH)₂),1.32(d,J＝7.2Hz,3H,2-Me)。¹³C{¹H}NMR(CDCl₃):205.53,154.61,152.68,147.07,133.89,117.86,115.50,43.17,35.72,34.88,34.69,23.30,16.43。

4, 5-dibromo-2-methyl-1, 6,7, 8-tetrahydro-as-benzodiindan-3 (2H) -one.

Measurement: c, 45.50; h, 3.77.

¹H NMR(CDCl₃):3.14(dd,J＝17.4Hz,J＝8.02Hz,1H,3-CHH’),3.06(t,J＝7.63Hz,2H,6-CH₂) 2.97 (Width t, J ═ 7.63Hz,2H, 8-CH)₂) 2.74(m,1H,2-H),2.48(dd, J ═ 17.4Hz, J ═ 4.0Hz,1H, 3-CHH'), 2.20 (quintuple, J ═ 7.63Hz,2H, 7-CH)₂),1.31(d,J＝7.43Hz,3H,2-Me)。¹³C{¹H}NMR(CDCl₃):205.13,152.93,150.21,141.48,133.91,123.51,119.50,43.03,36.86,32.26,31.20,23.95,16.48。

E)4, 8-dibromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzodiindene (indacene)

250ml of methanol were added dropwise to 117g (340mmol) of 4, 8-dibromo-2-methyl-3, 5,6, 7-tetrahydro-s-benzinden-1 (2H) -one and 19.3g (0.51mol) of NaBH by vigorous stirring at 0-5 ℃ over 5 hours₄In a mixture of 600ml of THF. The mixture was stirred at room temperature overnight and then evaporated to drynessAnd (5) drying. The residue was acidified to pH 5-6 with 2M HCl and the formed 4, 8-dibromo-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzodiindene-1-ol was extracted with 1200ml and then 2x200ml dichloromethane. The combined organic extracts were washed with Na₂SO₄Dried and evaporated to dryness. The resulting white solid was dissolved in 800ml of DMSO, and 90g (1.6mol) of KOH and 110g (0.775mol) of methyl iodide were added. The mixture was stirred at ambient temperature for 5 hours. The resulting solution was decanted from excess KOH, which was additionally washed with 3x 350ml dichloromethane. The combined organic extracts were washed with 3000ml of water. The organic layer was separated and the aqueous layer was extracted with 3x 300ml dichloromethane. The combined organic extracts were washed with 7 × 1500ml water and Na₂SO₄Dried and then evaporated to dryness. This procedure yielded 121g (99%) of 4, 8-dibromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzodiindene as a colorless thick oil that slowly crystallized at room temperature. The final material is a mixture of two stereoisomers.

For C₁₄H₁₆Br₂Analytical calculation of O: c, 46.70; h, 4.48. Measurement: c, 47.02; h, 4.69.

Cis-isomer:¹H NMR(CDCl₃) 4.60(d, J ═ 5.5Hz,1H,1-H),3.51(s,3H, OMe),2.87-3.08(m,5H, 3-CHH', 5-and 7-CH)₂) 2.74(dd, J15.9 Hz, J9.7 Hz,1H, 3-CHH'), 2.47(m,1H,2-H),2.09 (quintuple, J7.4 Hz,2H, 6-CH)₂),1.24(d,J＝6.85Hz,3H,2-Me)。¹³C{¹H}NMR(CDCl₃):146.01,144.83,144.22,143.06,116.75,116.22,86.86,59.05,40.65,39.29,35.44,35.38,23.45,13.56. Trans-isomer.¹H NMR(CDCl₃) 4.44(s,1H,1-H),3.43(s,3H, OMe),3.31(dd, J ═ 16.6Hz, J ═ 7.2Hz,1H, 3-CHH'), 2.95-3.05(m,4H, 5-and 7-CH) (₂) 2.57(m,1H,2-H),2.46(d, J ═ 16.6Hz,1H, 3-CHH'), 2.10 (quintuple, J ═ 7.6Hz,2H, 6-CH)₂),1.05(d,J＝7.2Hz,3H,2-Me)。¹³C{¹H}NMR(CDCl₃):146.49,144.67,144.01,140.71,117.41,116.70,92.32,56.83,40.62,36.89,35.40,35.23,23.53,19.81。

F) 4-bromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzodiindene

136ml (340mmol) of 2.5M in hexaneⁿBuLi was added dropwise over a period of 30min to a solution of 120.3g (334mmol) of 4, 8-dibromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzindene in 650ml of toluene cooled to-85 ℃. The resulting mixture was allowed to warm to-30 ℃ over 1 hour and stirred at that temperature for 30 min. The reaction was quenched with 200ml water, the yellowish organic layer was separated, and the aqueous layer was additionally extracted with 2 × 100ml dichloromethane. The combined organic extracts are washed with water₂CO₃Dried and then passed through a short layer of silica gel 60(40-63 μm). The silica gel layer was additionally washed with 50ml of dichloromethane. The combined organic effluents were evaporated to dryness and the crude product was distilled under reduced pressure to yield 87.2g (92.9%) of 4-bromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzindene (bp 147-.

For C₁₄H₁₇Analytical calculation of BrO: c, 59.80; h, 6.09. Measurement: c, 59.99; h, 6.20.

¹H NMR(CDCl₃) 7.13(s,1H,7-H),7.12(s,1H,7-H),4.51(d, J ═ 5.6Hz,1H,1-H),4.39(d, J ═ 3.8Hz,1H,1-H),3.42(s,3H, OMe),3.38(s,3H, OMe),3.17(dd, J ═ 16.4Hz, J ═ 7.6Hz,1H,3-CHH '), 2.97(t, J ═ 7.4Hz,4H, 5-and 7-CH'), respectively₂) 2.83(m,5H, 3-CHH', 5-and 7-CH)₂) 2.55-2.69(m,2H, two 2-hs), 2.51(m,1H,3-CHH '), 2.38(dd, J ═ 16.4Hz, J ═ 4.8Hz,1H, 3-CHH'), 2.08 (quintuple, J ═ 7.6Hz,4H, two 6-CH ═ s), 2.08 (quintuple, J ═ 7.6Hz,4H, two 6-CH)₂),1.15(d,J＝7.1Hz,3H,2-Me),1.09(d,J＝6.8Hz,3H,2-Me)。¹³C{¹H}NMR(CDCl₃):144.63,144.43,144.30,144.00,142.69,142.08,141.50,141.17,119.93,119.77,117.68,91.90,86.54,56.74,56.33,39.32,39.07,38.41,34.06,33.74,24.70,19.42,13.58。

2, g)4- (3, 5-di-tert-butylphenyl) -1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzindene

600ml (270mmol) of a 0.45M solution of 3, 5-di-tert-butylphenyl magnesium bromide in THF are added in one portion to 3.1g (3.97mmol) of NiCl₂(PPh₃) IPr and 56.4g (201mmol) 4-bromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzindene. The resulting solution was refluxed for 2 hours. After cooling to room temperature, 150ml of water were added to the reaction mixture and the major part of the THF was distilled off in a rotary evaporator. 500ml of dichloromethane and 1000ml of 1M HCl are added to the residue. The organic layer was separated and the aqueous layer was additionally extracted with 150ml dichloromethane. The combined organic extracts were evaporated to dryness to give a red oil. The product was isolated by flash chromatography on silica gel 60(40-63 μm; eluent: hexane-dichloromethane ═ 2:1, vol, then 1:1, vol). This procedure yielded 73.7g (94%) of 4- (3, 5-di-tert-butylphenyl) -1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzindene as a colorless thick oil as a mixture of two stereoisomers.

For C₁₄H₁₇Analytical calculation of BrO: c, 59.80; h, 6.09. Measurement: c, 60.10; h, 6.23.

Cis-isomer:¹H NMR(CDCl₃):7.34(t,J＝1.6Hz,1H,3,5-^tBu₂C₆H₃4-H) in (1), 7.23(s,1H, 7-H in indenyl), 7.16(d, J ═ 1.6Hz,2H,3,5-^tBu₂C₆H₃2,6-H) of (1), 4.49(d, J ═ 5.5Hz,1H,1-H of indenyl), 3.45(s,3H, OMe),2.96(t, J ═ 7.1Hz,2H),2.6-2.92(m,4H),2.54 (heptad, J ═ 6.5Hz,1H),1.94-2.11(m,2H, 6-CH), 2.4 (m,4H), 2.4 (eikont, J ═ 6.5Hz,1H), 2.11(m,2H, 6-CH)₂),1.34(s,18H,3,5-^tBu₂C₆H₃),1.09(d,J＝6.85Hz,3H,2-Me)。¹³C{¹H}NMR(CDCl₃):149.97,142.82,142.58,141.62,140.12,138.66,136.28,123.46,120.18,120.02,86.31,56.76,39.56,37.78,34.88,33.12,32.63,31.53,26.00,13.69. Trans-isomer:¹H NMR(CDCl₃):7.34(t,J＝1.76Hz,1H,3,5-^tBu₂C₆H₃4-H) in (1), 7.24(s,1H, 7-H in indenyl), 7.16(d, J ═ 1.76Hz,2H,3,5-^tBu₂C₆H₃2,6-H of (1), 4.39(d, J ═ 3.91Hz,1H, 1-H of indenyl), 3.49(s,3H, OMe),3.15(dd, J ═ 16Hz, J ═ 7.5Hz,1H, CHH'), 2.95(t, J ═ 7.24Hz,2H, 5-CH)₂),2.72-2.91(m,2H,7-CH₂),2.41-2.53(m,1H,2-H),2.3(dd,J＝16Hz,J＝4.8Hz,1H,CHH`),1.95-2.11(m,2H,6-CH₂),1.34(s,18H,3,5-^tBu₂C₆H₃),1.11(d,J＝7.0Hz,3H,2-Me)。¹³C{¹H}NMR(CDCl₃):149.99,143.29,142.88,140.91,139.33,138.62,136.31,123.39,120.18,120.01,91.56,56.45,40.06,37.89,34.87,33.09,32.58,31.52,26.02,19.31。

H)4- (3, 5-di-tert-butylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-benzodiindene

1.5g of TsOH was added to a solution of 73.7g (189mmol) of 4- (3, 5-di-tert-butylphenyl) -1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-benzindene (prepared as above) in 700ml of toluene and the resulting solution was refluxed with dean-Stark's head for 15 min. After cooling to room temperature, the reaction mixture was quenched with 200ml of 10% NaHCO₃And (4) washing with an aqueous solution. The organic layer was separated and the aqueous layer was additionally extracted with 2 × 150ml dichloromethane. The combined organic extracts were evaporated to dryness to give a yellowish crystalline material which was recrystallized from 250ml of hot n-hexane to give 48.2g of white crystalline product. Evaporating the mother liquor to dryness; the residue was recrystallized from 100ml of n-hexane to give a second crop (13.3g) of product. Thus, the total yield of 4- (3, 5-di-tert-butylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-benzindene isolated in this reaction was 61.5g (91%).

For C₂₇H₃₄The analytical calculation of (2): c, 90.44; h, 9.56. Measurement: c, 90.67; h, 9.74.

¹H NMR(CDCl₃):7.45(t,J＝1.76Hz,1H,3,5-^tBu₂C₆H₃4-H) of (1.76 Hz,2H,3,5-^tBu₂C₆H₃2,6-H in (1), 7.20(s,1H, 8-H in indenyl), 6.56(s,1H, indenyl)7-H) of (2), 3.28(s,2H, 5-CH)₂),3.06(t,J＝7.2Hz,2H,3-CH₂),2.90(t,J＝7.2Hz,2H,1-CH₂),2.17(s,3H,6-CH₂) 2.13 (quintuple, J ═ 7.2Hz,2H, 2-CH)₂),1.44(s,18H,3,5-^tBu₂C₆H₃)。¹³C{¹H}NMR(CDCl₃):150.17,145.58,144.91,143.02,139.85,139.15,138.01,135.26,127.07,123.19,120.24,114.82,42.23,34.92,33.29,32.27,31.56,25.96,16.80。

I) chloro [4- (3, 5-di-tert-butylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-benzinden-1-yl ] -dimethylsilane

2.5M in 10.0ml (25.0mmol) of hexaneⁿBuLi was added at room temperature to a solution of 8.96g (25.0mmol) of 4- (3, 5-di-tert-butylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-benzindene in a mixture of 200ml of toluene and 7.5ml of THF. The mixture was stirred at 60 ℃ for 2 hours. The resulting yellowish orange solution with a large amount of yellow precipitate was cooled to-60 ℃ and 16.1g (125mmol, 5 equivalents) of dichlorodimethylsilane were added in one portion. The resulting solution was stirred at room temperature overnight and then filtered through a frit (G3). The precipitate was washed with an additional 2 × 30ml of toluene. The combined filtrates were evaporated to dryness to give chloro [4- (3, 5-di-tert-butylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-benzodiindan-1-yl]Dimethylsilane, which is a yellowish glass, was used without additional purification.

¹H NMR(CDCl₃):7.39(t,J＝1.76Hz,1H,3,5-^tBu₂C₆H₃4-H) in (1), 7.32(s,1H, 8-H in indenyl), 7.25(d, J ═ 1.76Hz,2H,3,5-^tBu₂C₆H₃2,6-H) of (2, 6-H),6.60(s,1H, 3-H in indenyl), 3.59(s,1H, 1-H in indenyl), 2.94-3.08(m,2H, 7-CH)₂),2.83-2.99(m,2H,5-CH₂) 2.33(s,3H, 2-Me in indenyl), 2.07 (quintuple, J ═ 7.24Hz,2H, 6-CH)₂),1.39(s,18H,3,5-^tBu₂C₆H₃),0.47(s,3H,SiMeMe’),0.21(s,3H,SiMeMe’)。¹³C{¹H}NMR(CDCl₃) 150.02,144.41,142.13,141.54,139.92 (two resonance states), 138.78,131.41,127.01,123.94,120.14,118.64,49.78,34.89,33.32,32.51,31.57,26.04,17.72,1.26, -0.53.

J) [ 6-tert-butyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-2-methyl-1H-inden-1-yl ] [4- (3, 5-di-tert-butylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-benzodiindan-1-yl ] dimethylsilane

2.5M in 10.0ml (25mmol) of hexane at-50 deg.CⁿBuLi was added in one portion to a solution of 10.1g (25mmol) of 5-tert-butyl-7- (3, 5-di-tert-butylphenyl) -6-methoxy-2-methyl-1H-indene in 200ml of ether. The mixture was stirred at room temperature overnight, then the resulting yellow suspension was cooled to-50 ℃ and 250mg of CuCN was added. The resulting mixture was stirred at-25 ℃ for 30 minutes, then chloro [4- (3, 5-di-tert-butylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-benzinden-1-yl ] was added in one portion]A solution of dimethylsilane (prepared as above,. about.25 mmol) in 200ml of ether. The resulting mixture was stirred at ambient temperature overnight and then filtered through a pad of silica gel 60(40-63 μm), which was additionally washed with 2 × 50ml dichloromethane. The combined filtrates were evaporated to dryness and the residue was dried at high temperature in vacuo. This procedure gave 19.8g (97%) of a yellowish glass [ 6-tert-butyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-2-methyl-1H-inden-1-yl][4- (3, 5-di-tert-butylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-benzinden-1-yl]Dimethylsilane (confirmation of NMR spectra)>90% purity, an approximately 1:1 mixture of stereoisomers), which is further used without additional purification.

¹H NMR(CDCl₃):7.51(s),7.33-7.42(m),7.22-7.31(m),6.60(s),6.53(s),3.74(s),3.70(s),3.68(s),3.21(s),3.19(s),2.83-3.03(m),2.22(s),2.19(s),1.99-2.11(m),1.45(s),1.43(s),1.36(s),-0.16(s),-0.17(s),-0.21(s)。

K) dimethylsilylene [ eta ] s⁵-6-tert-butyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-2-methylinden-1-yl]-[η⁵-4- (3, 5-di-tert-butylphenyl) -2-methyl-5, 6, 7-trihydro-s-benzodiindan-1-yl]Zirconium dichloride

2.5M in 19.3ml (48.3mmol) of hexane at-50 deg.CⁿBuLi 19.8g (24.1mmol) of [ 6-tert-butyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-2-methyl-1H-inden-1-yl are added in one portion][4- (3, 5-di-tert-butylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-benzinden-1-yl]Dimethylsilane (prepared as above) in 300ml ether. The mixture was stirred at room temperature overnight. The resulting pale orange solution was cooled to-50 ℃ and 5.63g (24.2mmol) ZrCl was added₄. The mixture was stirred at room temperature for 24 hours. The resulting orange suspension was evaporated to dryness. The residue was dissolved in 250ml of warm toluene and the resulting hot suspension was filtered through a frit (G4). NMR spectroscopy confirmed that the resulting filtrate comprised about 1:1 of a mixture. The filtrate was concentrated to about 90 ml. The pale orange crystalline solid precipitated from the solution at room temperature overnight was filtered off, washed with 2 × 20ml of toluene, then 2 × 20ml of n-hexane, and dried in vacuo. This procedure yields 4.23g of trans-and cis-zirconocenes of about 83: 17 as a toluene mono-solvate. The mother liquor was further evaporated to about 60 ml. The reddish solid that precipitated from the solution at room temperature within 3 hours was filtered off and dried in vacuo. This procedure yielded 2.48g of cis-zirconocene as toluene mono-solvate. The mother liquor was evaporated to about 45 ml. The reddish solid that precipitated from the solution in 1 hour was filtered off and dried in vacuo. This procedure yielded 3.52g of cis-and trans-zirconocenes of about 93: 7 mixture which is a toluene mono-solvate. Again, the mother liquor was evaporated to about 35 ml. The light orange solid precipitated from the solution at room temperature overnight was filtered off and dried in vacuo. This procedure yielded 4.72g of trans-zirconocene as toluene monosolvate. Thus, trans-and cis-bis are isolated in this synthesisThe total yield of zirconocene (as toluene mono-solvate) was 14.95g (58%).

Trans-isomer.

For C₅₈H₇₆Cl₂OSiZr×C₇H₈The analytical calculation of (2): c, 72.85; h, 7.90. Measurement: c, 73.04; h, 8.08.

¹H NMR(CD₂Cl₂7.70 (width s,1H),7.60(s,1H),7.50(s,1H),7.43(s,1H),7.35-7.39(m,2H),7.33(t, J ═ 1.84Hz,1H),7.26(s,1H),6.75(s,1H),6.59(s,1H),3.30(s,3H),3.09-3.17(m,1H),2.91-3.00(m,2H),2.78-2.85(m,1H),2.18(s,3H),2.16(s,3H),2.03-2.12(m,1H),1.90-2.00(m,1H),1.39(s,9H),1.31-1.37(m,27H),1.30 (m,3H), 1.28(s, 9H).¹³C{¹H}NMR(CD₂Cl₂,-20℃):159.78,150.82,150.67,150.06,149.53,144.49,143.69,142.90,137.35,135.70,135.03,133.54,133.48,132.88,132.56,127.36,126.94,124.67,124.41,124.03,123.22,122.90,121.62,121.02,120.61,120.55,120.10,117.81,81.58,81.01,62.42,35.68,35.10,34.98,34.82,33.12,32.37,31.48,31.38,30.29,26.58,18.38,2.62,2.54。¹The resonance states attributed to toluene are removed from this description of the NMR spectrum.

The cis-isomer.

Measurement: c, 73.15; h, 8.13.

¹H NMR(CD₂Cl₂7.82 (width s,1H),7.71(s,1H),7.51(s,1H),7.41(s,1H),7.35(t, J ═ 1.84Hz,1H),7.33(t, J ═ 1.84Hz,1H),7.29(s,1H),7.24 (width s,1H),6.74(s,1H),6.53(s,1H),3.11(s,3H),3.04-3.10(m,1H),2.76-2.91(m,3H),2.39(s,3H),2.37(s,3H),1.99-2.06(m,1H),1.63-1.75(m,1H),1.44(s,3H),1.38 (width s,9H),1.34(s,9H), 1.31 (s,1H), 9.31H (s, 31H), 31.31H).¹³C{¹H}NMR(CD₂Cl₂,-20℃):158.77,150.64,150.10,149.61,143.44,142.74,141.74,136.87,136.30,135.68,135.29,135.17,134.33,131.59,126.50,124.38,124.08,124.03,123.65,123.36,121.55,121.04,120.90,120.84,120.15,118.34,82.86,82.72,62.12,35.44,35.12,34.97,34.79,33.17,32.48,31.45,31.42,30.13,26.77,18.63,18.55,2.87,2.68。²Resonance state from N ascribed to tolueneRemoved from this description of MR spectroscopy.

3. Complex 3-Zr: racemic dimethylsilylene bis- (2-isobutyl-4- (4' -tert-butylphenyl) -5,6, 7-trihydro-s-benzinden-1-yl) zirconium dichloride (C3-Zr)), catalyst 1 was prepared as described in patent application WO2012/001051a 1.

b) Catalyst system

Comparative example 1

Preparation of comparative catalyst System CCS-1 Using the racemic Complex 1-Zr

C1-Zr had been prepared according to the method described in WO2013/007650A1 for catalyst E2 by adjusting the amounts of metallocene and MAO to achieve the Al/Zr ratio indicated in Table 1. The complex has been prepolymerized off-line with propylene according to the method described in WO2013/007650A1 for catalyst E2P.

The off-line prepolymerization degree is 3.3 g/g.

The Al/Zr molar ratio in the catalyst was 431 mol/mol.

The metallocene complex content in the off-line prepolymerised catalyst was 0.696 wt%.

Embodiment 1 of the present invention:

preparation of the catalyst System ICS-1 of the invention Using the racemic Complex 1-Zr

And (1).

In a glove box, 87.90mg of rac-C1-Zr prepared above was mixed with 4ml of 30 wt% Chemtura MAO in a septum bottle, the solution was stirred for 60 minutes, and 105.2mg of trityl tetrakis (pentafluorophenyl) borate was added. The mixture was reacted in a glove box at room temperature overnight. Then, in another septum bottle, 54 μ Ι _ of dried and degassed FluorN474 was mixed with 2mL of 30 wt.% Chemtura MAO. The solution was stirred overnight.

The following day, 4mL of MAO-metallocene-borate solution and 1mL of surfactant-MAO solution were added successively to a 50mL emulsified glass reactor containing 40mL of PFC at-10 ℃ and equipped with an overhead stirrer (stirring speed 600 rpm). The total amount of MAO was 5mL (200 equivalents). A red emulsion was formed immediately (measured emulsion stability ═ 19 seconds) and stirred at-10 ℃/600rpm for 15 minutes. The emulsion was then transferred to 100mL of hot PFC at 90 ℃ through an 2/4 polytetrafluoroethylene tube and stirred at 600rpm until the transfer was complete. The speed was then reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer was turned off. The catalyst was settled on top of the PFC and after 35 minutes the solvent was siphoned off. The remaining red catalyst was dried at 50 ℃ for 2 hours in a stream of argon. 0.86g of a red powder with good flowability (31.2 wt% for Al and 0.49 wt% for Zr) was obtained.

Off-line prepolymerization step

The off-line prepolymerization experiment was carried out in a 125mL pressure reactor equipped with a gas feed line and an overhead stirrer. Dried and degassed perfluoro-1, 3-dimethylcyclohexane (15 cm)³) And 0.6855g of the catalyst prepared in step 1 (to be prepolymerized) were charged into a reactor in a glove box, and the reactor was sealed. The reactor was then removed from the glove box and placed in a water cooling bath maintained at 25 ℃. The overhead stirrer and feed line were connected and the stirring speed was set to 450 rpm. The experiment was started by opening the propylene feed to the reactor. The total pressure in the reactor was raised to about 5 bar and kept constant with the propylene feed by mass flow controllers until the target degree of polymerization (DP ≈ 4.0) was reached. The reaction was stopped by flashing off the volatile components. Inside the glove box, the reactor was opened and the contents poured into a glass container. Perfluoro-1.3-dimethylcyclohexane was evaporated until a constant weight was obtained to yield 3.42g of prepolymerized ICS-1 catalyst.

Embodiment 2 of the present invention:

preparation of the catalyst System ICS-2 of the invention Using the racemic Complex 1-Zr

88.03mg of complex 1-Zr were mixed with 5ml of MAO in a septum bottle inside a glove box, the solution was stirred for 60 minutes, then 105.15mg of trityl BF20 were added. The mixture was allowed to react overnight at room temperature in a glove box. (preparation method according to the above step 1, without prepolymerization step)

Embodiment 3 of the present invention:

preparation of the catalyst System ICS-3 of the invention Using the racemic Complex 2-Zr

111,65mg of complex 2-Zr were mixed with 5ml of MAO in a septum bottle inside a glove box, the solution was stirred for 60 minutes, then 105.15mg of trityl BF20 were added. The mixture was allowed to react overnight at room temperature in a glove box. (preparation method according to the above step 1, without prepolymerization step)

Embodiment 4 of the present invention:

preparation of the catalyst System ICS-4 of the invention Using the racemic Complex 3-Zr

Inside a glove box, 103,21mg of complex 3-Zr were mixed with 5ml of MAO in a septum bottle, the solution was stirred for 60 minutes, then 105.15mg of trityl BF20 were added. The mixture was allowed to react overnight at room temperature in a glove box. (preparation method according to the above step 1, without prepolymerization step)

Embodiment 5 of the present invention:

preparation of the catalyst System ICS-5 of the invention Using the racemic Complex 3-Zr

68.80mg of complex 3-Zr were mixed with 4ml of MAO in a septum bottle inside a glove box and the solution was stirred for 60 minutes. The mixture was allowed to react overnight at room temperature in a glove box. (preparation method according to the above step 1, without prepolymerization step)

Table 1: catalyst system composition

Catalyst and process for preparing same	Metallocenes	DofP¹	Al/Zr²	B/Zr³
							[g/g]	[mol/mol]	[mol/mol]
CE-1	C1-Zr	3.3	431	0.0
					IE-1	C1-Zr	4.0	215	1.0
IE-2	C1-Zr	n.a	200	1.0
					IE-3	C2-Zr	n.a	200	1.0
IE-4	C3-Zr	n.a	200	1.0
					IE-5	C3-Zr	3.9	300	0.0

¹Off-line pre-polymerization degree

²Molar ratio of Al/Zr in the catalyst

³B/Zr molar ratio in the catalyst

n.a does not apply

Polymerisation

To demonstrate the applicability of the catalyst system according to the present invention, two polymerization reactions were carried out.

In examples IE-1, IE-5 and CE-1, the polymerization was carried out in a 480mL pressure reactor at 110 ℃.

In examples IE-2, IE-3 and IE-4, the polymerization was carried out in a Parallel Polymerization Reactor (PPR) (supplied by Symyx) (10mL reactor volume) at 190 ℃.

Aggregation methods IE-1, IE-5 and CE-1:

catalyst systems ICS-1 and ICS-5 were used, and catalyst system CCS-1 was used as a comparative example (all prepared as described above)

Ethylene/1-octene solution polymerization in heptane at 110 ℃ in the absence of H according to the following procedure₂Under the conditions of (1).

First, the required amount of 1-octene was fed into the reactor by a Waters HPLC pump, followed by 200mL heptane by a 10mL syringe. The stirring speed was set to 150 rpm. 50 μmol Triethylaluminium (TEA) as scavenger was fed to the reactor as a 0.5mol/L heptane solution. The reactor temperature was set at 110 ℃. Ethylene was fed to the reactor up to the desired pressure (P ═ 20 bar) and the desired amount of catalyst was injected at the polymerization temperature. The pressure was kept constant, ethylene was fed and after 20min polymerization time the catalyst was deactivated by adding air and evacuating the reactor. The sample was stabilized with 2500ppm Irganox B225 (dissolved in acetone).

Table 2: results of ethylene/1-octene solution copolymerization

Prepolymerized

n.m. unmeasurable

As is clear from the table, if an additional borate cocatalyst is used, or if a special complex is used, where R is⁵And R⁶Both and R^5′And R^6′Form an unsubstituted 5-membered ring fused to the phenyl ring of the indenyl moiety, and R²And R^2′Is not C₁Alkyl groups, the productivity of the catalyst system is increased. The latter additionally showed a very high comonomer insertion also in the absence of additional boron co-catalyst.

PPR aggregation methods and characterizations for IE-2, IE-3, and IE-4

Preparation of precatalyst (ternary system MC/MAO/tritylBF 20):

in a glove box, the desired amount of metallocene was mixed with 5ml of MAO solution in a septum bottle, the solution was stirred for 60 minutes, then 105.15mg of trityl BF20 was added. The mixture was allowed to react overnight at room temperature in a glove box.

All catalysts were prepared according to the following formulation (table 3).

Table 3: pre-catalyst preparation of selected metallocenes

Examples	IE-2	IE-3	IE-4
				C1-Zr[mg]	88.03
C2-Zr[mg]		111.65
				C3-Zr[mg]			103.21
MAO[mg]	1320	1320	1320
				TritylBF20[mg]	105.15	105.15	105.15
Al/Zr	200	200	200
				B/Zr	1.0	1.0	1.0

MAO was used as a 30% solution in toluene.

Polymerization process for PPR:

the selected catalyst was screened at 190 ℃ using the polymerization solvent decane, an MAO/Zr ratio (200), a B/Zr ratio (1.0) and 1 w/w (C)₈/C₂1.0 w/w) of 1-octene/ethylene.

Stock solutions of metallocene and cocatalyst (MAO and borate) were prepared for each set of reactions.

The containers were loaded into the glove box using a 3-axis liquid handling robot. A pre-weighed glass vial with a stir paddle was sealed and purged with nitrogen. A volume of about 4mL of the corresponding solvent (decane) was packed in each PPR reactor. Then, sufficient Triethylaluminum (TEA) was added as a scavenger at room temperature, along with a precise volume of octene as a comonomer. The ethylene pressure was set to 10 bar to check for any leaks. Then, the temperature and pressure were raised to the set values (T190 ℃ and 24 bar), and once the steady state was reached, the corresponding volume of preactivated catalyst was injected into the reactor as a slurry in toluene with mechanical stirring to start the polymerization reaction. After a set amount of ethylene uptake has been reached, with CO₂The reaction run was quenched (20min for maximum run time). The glass vial has been dried by a vacuum centrifuge and weighed.

Table 4: PPR experimental conditions for ethylene/1-octene solution copolymerization

	ICS-2	ICS-3	ICS-4
				Catalyst System [ mu.l]	51.8	35.7	38.7
1-octene used [ g ]]	0.45	0.45	0.45
				Decane [ g ]]	3.14	3.16	3.16
TEAL scavenger [ mu mol ]]	15.0	15.0	15.0

Table 5: PPR experimental result of ethylene/1-octene solution copolymerization

n.m. is not measurable.

Claims

1. A catalyst system for the preparation of ethylene copolymers in a high temperature solution process, said catalyst system comprising

(i) Metallocene complexes of the formula (I)

Wherein

M is the component of Zr,

x is independently a hydrogen atom, a halogen atom, C_1-6-alkoxy groups or R¹¹Group, wherein R¹¹Is C_1-6-an alkyl group, a phenyl group or a benzyl group,

R¹and R^1′Identical or different and are straight-chain or branched C₁-C₄-an alkyl group,

R⁷and R^7′Are the same and are H;

wherein

a) n is 1 or 2, and n is a hydrogen atom,

and R is⁵And R⁶Or R⁵' and R^6′For R⁵Or R⁵' is an OR group, wherein R is C₁-C₄-an alkyl group, and for R⁶Or R⁶' is C (R)¹⁰)₃Group, wherein R¹⁰Are identical and R¹⁰Is C₁-C₂-an alkyl group;

or

b) n is 1 or 2, and n is a hydrogen atom,

R²and R^2′Are the same and are CH₂-R⁹Group, wherein R⁹Is straight chain or branched C₁-C₄-an alkyl group,

R⁵and R⁶And R⁵' and R^6′Together form an unsubstituted 5-6 membered ring fused to the phenyl ring of the indenyl moiety;

or

c) n is 0,1 or 2, with the proviso that for only one of the phenyl groups and not for both phenyl groups, n is 0,

R²and R^2′Are the same and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C₁-C₄-an alkyl group,

R⁵and R⁵' same OR different and is H OR OR group, wherein R is C₁-C₄-an alkyl group,

R⁶and R^6′Identical or different and is H or C (R)¹⁰)₃Group, wherein R¹⁰Are the same or different and R¹⁰Is straight chain or branched C₁-C₄-an alkyl group,

wherein at least one of the indenyl ligands is unsubstituted at the 5-and 6-positions;

(ii) an aluminoxane cocatalyst; and

(iii) a boron-containing promoter.

2. The catalyst system according to claim 1, wherein in the formula (I)

n is 1 or 2, and n is a hydrogen atom,

and R is⁵And R⁶Or R⁵' and R⁶The remaining residue of' for R⁵Or R⁵' is an OR group, wherein R is C₁-C₄-an alkyl group, and for R⁶Or R⁶' is C (R)¹⁰)₃Group, wherein R¹⁰Are identical and R¹⁰Is C₁-C₂-an alkyl group.

3. The catalyst system according to claim 1, wherein in the formula (I)

n is 1 or 2, and n is a hydrogen atom,

R⁵and R⁶And R⁵' and R^6′Together form an unsubstituted 5-6 membered ring fused to the phenyl ring of the indenyl moiety.

4. The catalyst system according to claim 1, wherein in the formula (I)

L is of the formula-SiR⁸ ₂A bridge of (a) wherein two R are⁸Is the same C₁-C₁₀-a hydrocarbyl group or C₆-C₁₀-an aryl group,

n is 0,1 or 2, with the proviso that for only one of the phenyl groups and not for both phenyl groups, n is 0,

R⁵and R⁵' same or differentAnd is H OR OR group, wherein R is C₁-C₄-an alkyl group,

wherein at least one of said indenyl ligands is unsubstituted at the 5-and 6-positions.

5. The catalyst system according to any one of claims 1 to 4, wherein the metallocene of formula (I) is selected from those in their cis or trans configuration

Racemic dimethylsilylene [ eta ]⁵-6-tert-butyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-2-methylinden-1-yl][η⁵-4- (3, 5-di-tert-butylphenyl) -2-methyl-5, 6, 7-trihydro-s-benzodiindan-1-yl]Zirconium dichloride or zirconium dimethyl,

Or is selected from

Trans-dimethylsilylene (2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl) (2-methyl-4- (4-tert-butyl-phenyl) indenyl) zirconium dichloride.

6. The catalyst system of claim 1 or 2, wherein the aluminoxane cocatalyst is MAO.

7. The catalyst system of claim 1 or 2, wherein the boron-containing promoter comprises an anion of the formula:

(Z)₄B^-(III)

wherein Z is an optionally substituted phenyl derivative, said substituent being halo-C_1-6-an alkyl group or a halogen group.

8. The catalyst system of claim 7, wherein the boron-containing promoter is

Triphenylcarbenium tetrakis (pentafluorophenyl) borate,

n, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate,

n, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate, or

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

9. A metallocene complex of the formula (I),

wherein

M is the component of Zr,

x is a Cl or methyl group,

n is 1 or 2, and n is a hydrogen atom,

and R is⁵And R⁶Or R⁵' and R⁶The remaining residue of' for R⁵Or R⁵' is an OR group, wherein R is C₁-C₄-an alkyl group, and for R⁶Or R⁶' is C (R)¹⁰)₃Group, wherein R¹⁰Are identical and R¹⁰Is C₁-C₂-an alkyl group,

R⁷and R^7′Is the same as and is H.

10. A catalyst system according to claim 1 obtainable by a process wherein

(a) (iv) forming a liquid/liquid emulsion system comprising a solution of catalyst components (i) to (iii) dispersed in a solvent to form dispersed droplets; and

(b) solid particles are formed by solidifying the dispersed droplets.

11. The catalyst system according to claim 10, wherein the solid particles are prepolymerized in step (c).

12. The catalyst system according to claim 10 or 11, wherein the catalyst system is an unsupported catalyst system obtainable by contacting the metallocene of formula (I) as a solid or in solution with a cocatalyst previously dissolved in an aromatic solvent, or by sequential addition of the catalyst components to the polymerization medium.

13. The catalyst system of claim 10 or 11, wherein the aluminoxane cocatalyst is MAO.

14. The catalyst system of claim 10 or 11, wherein the boron-containing promoter comprises an anion of the formula:

(Z)₄B^-(III)

15. The catalyst system of claim 14, wherein the boron-containing promoter is

Triphenylcarbenium tetrakis (pentafluorophenyl) borate,

n, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate,

n, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate, or

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

16. Use of a catalyst system as described below or a metallocene complex as defined in claim 9 in the polymerisation of olefins in a high temperature solution process at a temperature above 100 ℃ for the polymerisation of ethylene and C_4-10Polymerizing an alpha-olefin comonomer to produce a polyethylene, wherein the polyethylene has

a) A comonomer content measured by NMR of up to 40% by weight,

b) at 0.850g/cm³To 0.950g/cm³Densities within the range measured according to ISO 1183 and 187,

c) Mw/Mn values measured by GPC of less than 5, and

d) a melting point measured by DSC according to ISO 11357-3:1999 of less than 130 ℃,

wherein the catalyst system comprises

(i) Metallocene complexes of the formula (I)

Wherein

M is Hf or Zr,

x is a sigma ligand,

n is 0,1 or 2,

R¹and R^1′Identical or different and are straight-chain or branched C₁-C₆-an alkyl group,

R²and R^2′Are the same or different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C₁-C₆-an alkyl group,

R⁵and R⁵' same or differentAnd is H or straight or branched C₁-C₆-an alkyl group OR an OR group, wherein R is C₁-C₆-an alkyl group,

R⁶and R^6′Identical or different and is H or C (R)¹⁰)₃Group, wherein R¹⁰Are the same or different and R¹⁰Is H or straight or branched C₁-C₆-an alkyl group,

and

R⁷and R^7′Identical or different and are H or straight-chain or branched C₁-C₆-an alkyl group;

(ii) an aluminoxane cocatalyst; and

(iii) a boron-containing promoter.

17. Use according to claim 16, wherein the comonomer content of the polyethylene is between 5 and 40 wt%.

18. Use according to claim 16, wherein the polyethylene has a density of 0.850g/cm³To 0.945g/cm³Within the range.

19. Use according to claim 16, wherein the Mw/Mn of the polyethylene is in the range of 2.0 to 4.5.

20. Use according to claim 16, wherein the polyethylene has a melting point below 120 ℃.

21. Use according to any one of claims 16 to 20, wherein the comonomer is butene, hexene or octene.

22. A process for the preparation of an ethylene copolymer, said process comprising contacting ethylene and C in the presence of a catalyst in a high temperature solution process at a temperature above 100 ℃_4-10An alpha-olefin comonomer polymerization, said catalyst comprising:

(i) a metallocene complex of the formula (I),

wherein

M is Hf or Zr,

x is a sigma ligand,

n is 0,1 or 2,

R⁵and R⁵' same or different and is H or straight or branched C₁-C₆-an alkyl group OR an OR group, wherein R is C₁-C₆-an alkyl group,

or R⁵And R⁶And/or R^5′And R⁶' together form an indenyl group fused toAn unsubstituted 4-7 membered ring on part of the phenyl ring, provided that if R⁵And R⁶And R^5′And R⁶' together form an unsubstituted 5-membered ring fused to the phenyl ring of the indenyl moiety, then R²And R^2′Is other than C₁-an alkyl group;

and

(ii) an aluminoxane cocatalyst, and

(iii) a boron-containing promoter.

23. The process according to claim 22, wherein the polymerization is carried out at a) a polymerization temperature of at least 110 ℃, b) a pressure in the range of from 10 to 100 bar, and C) at a temperature selected from unsubstituted or substituted by C_1-4Alkyl radical substituted C_5-12-in a liquid hydrocarbon solvent of the group of hydrocarbons.